Removal of alkali from alumina



Patented Aug. 9, 1949 REMOVAL OF ALKALI FROM ALUMINA Miroslav W. Tamele, Oakland, Vanan C. Irvine, Richmond, and James F. Mahar, Berkeley, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation Delaware No Drawing. Original application February 1943, Serial No. 476,032. Divided and this ap plication February 10, 1948, Serial No. 7,528

6 Claims. vl.

This application is a division of copending application Serial Number 476,032, filed February 15, 1943, now Patent No. 2,454,724, issued November 23, 1948.

This invention relates to a new and improved method for the removal of alkali impurities from alumina and to the preparation of improved molybdena alumina catalysts with the purified alumina so produced.

A great number of substances having large available surfaces have been used or suggested as supports for molybdenum oxide. 03 the numerous materials available, alumina, due to its marked superiority in certain respects, is a particularly excellent carrier the superiority of alumina over other carrier materials is due largely to its superior stabilizing and promoting properties in combination with a large inner surface, moderately good thermal stability, and availability. Alumina, it is found, is especially effective in stabilizin the activity of catalytic promoters deposited thereon. According to A. Mittasch and E. Keunecke [Z. Elektrochem 38, 666 (1932) l, the stabilizing effect of alumina is due primarily to the fact that the somewhat porous inter-layers of alumina prevent the recrystallization or sintering of the active catalyst.

Although alumina is recognized as the best carrier or extending material for molybdenum oxide, it is well known that all aluminas are not equivalent and that some are not suitable. The aluminas employed in such catalysts are invariably activated, 1. e. adsorptive, aluminas. Aluminas ordinarily contain considerable amounts of combined water. By suitably heating the alumina to drive out a portion oithe water, small pores are opened up in the interior, and it becomes adsorptive. It is then said to be activated. Alpha alumina, for example, which is the corundum form, contains little or no inner surface, cannot be activated, and .is unsuitable. Also, the alumina beta monohydrate, which has never been synthetically prepared but occurs in nature as the mineral diaspore, is likewise very inferior. The alumina beta monohydrate, diaspore, has little adsorptive capacity and, if heated to drive off part of its water, it is converted directly to inactive alpha alumina. Suitable activated aluminas, on the other'hand, may be prepared from the gamma aluminas oi the Haber system. Haber [Naturwiss 13, 1001 (1925)] classifies the various forms of alumina into two systemsdesignatedzby him as the gammaand beta systems, according to their behavior upon heating. The gamma aluminas of the Haber classification comprise gamma alumina and the socalled hydrated aluminas which, upon heating, are converted to alpha alumina through the gamma form. The aluminas which, upon heating, are converted into alpha alumina through gamma alumina and belong to the gamma system of the Haber classification are:

The alumina alpha trz'hydrate, known as gibbsite or hydrargillite.-This form is readily prepared synthetically and occurs in nature in the mineral gibbsite and as a component of certain bauxites;

The alumina beta trz'hydrate, known also as bayrite.-It ,is isomorphous with hydrargillite. It does not occur naturally, but may be prepared synthetically by proper control of the precipitation conditions;

The alumina alpha monohydrate, known as bcihmite.--This alumina is formed by the partial dehydration of either of the above two trihydrates;

Galatinous aluminum hydraccide.This frequently encountered alumina is amorphous when freshly precipitated, but after aging the characteristic lines of btihmite can be detected by X-ray analysis. On further. aging, the precipitate is gradually transformed to bayerite and finally to hydrargillite;

Bauxite-.This ore is of varied composition. The term bauxite was usedin the older literature to designate the dihydrate. It is now known that bauxite consists of an extremely finely divided mixture of two ormore of the known aluminas and certain argillaceous residues. No dihydrate of alumina has ever been observed.

Gamma alumina.-This is a meta-stable anhydrous oxide which cloes-not occur naturally, but may be prepared by carefully controlled dehydration of any of the above-mentioned hydrates.

While the mentioned gamma aluminas oi the Haber system yield adsorptive aluminas from which highly active molybdena-alumina catalysts may bgprepared, some of these are much superior to others. The best catalysts are usually prepared from adsorptive aluminas prepared by dehydrating (activating) alumina trihydrate which'has been crystallized from alkaline aluminate solutions; Thecatalysts prepared with ad sorptive aluminas obtained by dehydration of alumina 'trihydrate crystallized from allraine aluminate solutions :arehighly active, stable to mechanical degradation, and are quite stable catalytically. They. maybeqused for, long, periods of time before losing their activity. These ex- 3 cellent properties of the molybdena catalysts so prepared are definitely traceable to the particular type of alumina used.

It has been suspected that these superior prop erties are due to at least two fundamental characteristics of this particular type of alumina. The first of these is the high mechanical strength of the alumina produced in the described manner. This matter of strength of the catalyst is very important since during use the strength tends to decline and unless a catalyst of very high initial mechanical strength is employed it is apt to crumble when used in large beds. Failure of the catalyst strength produces fines, causes plugging, channeling, etc. and is very undesirable. The second characteristic is that'the aluminas produced as described invariably contain appreciable amounts of impurities such as, in particular, sodium salts. The sodium is intimately associated with the alumina due to its method sponsible for its superiority as a constituent of 11- the catalysts ofthe type in question. It is well known that small amounts of the alkali metals are highly beneficial in many related catalysts. Thus, for example, small amounts of sodium are known to promote the water gas reaction I with similar metal oxide catalysts such as the oxides of iron, cobalt, nickel, chromium, etc. The presence of the sodium, therefore, no doubt is beneficial in the regeneration of the catalyst and also probably allows a certain amount of carbon removal from the catalyst during use by reaction with traces of water. Thus, for example, it is known that small percentages of sodium in chrome-alumina and molybdenaalumina catalysts decrease the carbon deposition and it has been recommended that the alumina carrier be alkalized with about 1% of sodium oxide prior to incorporating the molybdenum oxide. It is also well known that small amounts of alkali metals greatly promote the dehydrogenation and dehydrocyclization activity of the closely related iron-alumina and chrome-alumina catalysts. Aside from the above-mentioned prorioting effects, there is reason to expect the presence of the sodium or other alkali metal in the preferred alumina of this particular type to be beneficial in still a diiferent respect. Thus, adsorptive aluminas, when subjected to relatively elevated temperatures, gradually revert into the stable alpha modification which, as explained above, is unsuitable for these catalysts. This transformation takes place at appreciable rates only at temperatures of the order of 900 C. to 1000 C. or above. At lower temperatures such as are usually employed in catalytic processes this conversion is quite slow, but nevertheless takes place over extended periods of time. It is also found that in the presence of molybdenum oxide the undesirable conversion takes place at appreciable rates at lower temperatures. The first step of the accelerated transformation appears to be the formation of a definite molybdena-alumina compound which then breaks down easily into molybdenum oxide and alpha alumina. X-ray studies have shown that the deactivation of the molybena-alumina catalysts in use is largely due to this transformation. It has also been shown by X-ray studies that the preferred particular type of alumina containing sodium is more diffetical respects.

4 cult to convert to the alpha modification by heat ing than are other aluminas.

It is to be particularly emphasized that the effect of sodium on the thermal stability of gamma alumina is distinctly and entirely different from its effect upon the thermal stability of silica gels or hydrous aluminum silicates. In preparing siliceous catalysts (particularly the highly developed silica base catalysts for cat alytic cracking), it is known that even very small traces of alkali metal salts are very detrimental. In this case, however, the sodium salts act as a flux and cause a great decrease of the active inner surface due to simple sintering.

Of the adsorptive aluminas prepared by dehydration of aluminas precipitated from alkali aluminate solutions, the massive variety (as distinguished from the powders) obtained by certain crystallization methods is .by far the best for use in preparing molybdena-alumina catalysts and is the variety presently used commercially. This variety of alumina is readily obtained in massive fragments of suitable size for use in catalysis. Suitable sizes are, for example, 4 to 8 mesh and 2 to 4 mesh.

In order that the importance of the variations in the method of catalyst preparation may be readily appreciated, it is desirable to indicate the method of preparation hitherto employed and the reasons for the adaptation in practice of this particular method. In the art, and particularly the patent art, a variety of methods have been indicated as possible (and substantially equivalent as far as the properties of the catalyst are concerned) for the preparation of the general class of metal oxide dehydration catalysts. Thus, there are' described various methods of impregnating a wide variety of carrier materials as well as various co-precipitat1on methods. Although it might be assumed from the teachings of such art that these various methods would be applicable and would afford equivalent catalysts, several practical considerations have hitherto excluded all but one method. In the method presently practiced the adsorptive alumina carrier is impregnated with a solution of a suitable molybdenum compound such as, for example, ammonium molybdate. Adsorptive aluminas vary somewhat from batch to batch in adsorptive ability, depending upon the degree .of ammonium molybdate solution that the entire solution is adsorbed in the alumina. Since all of the molybdenum applied is taken up by the alumina particles, the concentration of molyb dena in the catalyst may be easily controlled by adjusting the amount of molybdenum applied,

and no variation in the catalyst composition is caused by any irregularities in the degree of activation of the alumina. This method is also considered advantageous in several other prac- Thus, by this method the molybdena is largely concentrated near the macro surface of the alumina particles. The catalyst is used in the form of pieces of suitable size, for example, 2 to 4 mesh pieces. The reaction therefore takes place largely near the surface, and the carbonaceous deposits are largely concentrated near the macro surface. The regeneration is therefore more easily eifected in a shorter time since carbonaceous matter which is deposited near the center of .the catalyst particles pioyed, these impurities; a ,monium -molybdate -.-solu least toa certa n extent, suchore .ticular feed and the particular conditions. reaction-which is usually important is the dehydrogenation of hydroaromatic hydrocarbons to their corresponding aromatic hydrocarbons. Another re c i which s nere l -ris alli a m portant,isdehydrocyclization. "Another reaction which usually takesplace.wnenlreatinasuliu containing feeds is 4 hydrogenation of the sulfur is difiicult .to -remove--and.- re uires. arslongeburning w with .7 higher-'than-usual concentrations 30f oxygen. Another L advantage. of :the described method is that it avoids contaminationaohthe catalyst and waste of molybdenum. Thus, the

um m lo ,d,..u ua h contain rec s to appreciable vconc entrations;.of; impurities. Iran exce s o mmoniu a qlxbs ie c aim-= gm" moni b hs at so ntic cthere a e m st .Elq d carded o used-ri se cpntemiea edceqeditio iorithe nex --batc ;of;cata

.. dehydro enation-cf orean criccmpeundstz hedehydoocyclizationv of parafiin --hy! .1. %rbonsto aromatic ,-hydrocarbens,- .t-he dehydroisornecization of such compoundsas-rmcthylcyclopentane, dimethyl cyclopentaner: ethyl cyclopentane,- etc. directly to aromatic hydrocarbons; the-hydrogenation of various unsaturated organic com-- pounds, the isomerization of :isomerizable .paraffin .hydrocarbons-the-i desuliurization 1 of. sulfurbearing hydrocarbon fractions; the destructive hydrogenation of rhigh molecular weight .car-

bona'ceous materials athe .oxidation- .of I organic compounds, and the dike, .these -yersatile..catalysts have been =widely--experimented with and 4 as ro u f act on .bQ1line.-.=- iti1invthe ne lin boi i ea eei nt c ranenr a Ge co ditions of e vat t mperature;andnre surei the presence of: added hydrogen and a molybdone-alumina catalyst 9f :the gtype described, thereby eff ct certainedes rabl chang :i the hydrocarbon treated. rThe conditlons are so; chosen that no substantial; a nountrof destructiverhydrogenationtakea Place. *.;;In the process of the hydroforrning, various types of reactions can, and usually'do, take place to various extents, depending somewhat uponthe par- One compoundsto I hydrogen--sulfide. =Uneler-seme conditions, depending-upon the hydrogen pressure and temperature, a-certain amoimtof-hyidlogenaftlon of oleflns may take place. Although hydroforining is not usually conducted for the purpose of producing cracking, a small amount of cracking usually does take place. Although hydroforrning .may .beapnlied advantageously to a largenumber---of--- materials;-- its -mere -impcrtant uses. are for thenimprovement-eof the 'tions.

In the process of hydroforming the hydrocarbon or hydrocarbon fraction togbe hydroformed is vaporized and the-vaporsare-contacted in' the 85ffresh catalyst.

--.-presence. of added hydrogen .undqr 1hxdmermin conditions with a. suitable rdehydro cnationzzicatf -aiyst. The ternperatures; .applieddepend somewhat .upon the .feed .and .uponzth-e .otherafactoxjs involved but. are-usually between. aboutAOEPfl. and:525 .C. The-process is generally carriedput at superatmosphericpressures-which are,;ho.vv.- ever, in no case sufficiently highzao..cause.isubstantial ..destructive zhydrogenation. "Suitable l0 pressures vary, for .instance,--between.abouti2 and ,40 atmospheres. :Th contact time depend seupon the particular economiesof rtheeplantp-unonthe activity of the .cataly st,-. uponzthezieemetc. wfrhus, the liquid hourly space velocity may varysfroin ,15 between-about 11.3 and1'2. :Inorder supply a suitablepartial pressure of hydrogenrhydrogensis --addedin a ratio of from; aboutv' .1 1 111015 0cm. drogen per rnol of hydrocarbon-awed toeabont 30:1-mols"of hydrogen per-mol ofhydrocarbon .20 feed. During-use thex-activi-tyeofethe -...ca,ta'lyst declines relatively rapidly: dueto thexleposition thereon of carbonaceous matter. It.-is therefore *the practice-to stop the hydroforming atzfrequent intervals, flush-1 the catalyst :of hydrogen -..and

hydrocarbon -vapors,'- and eburn .ofi-sthe carbonaceous :deposit's at-atmospheric. or.--super-atmospheric pressure with -a carefully icontrolled stream of gas containing a--controlled concentration 0J5 oxygen or otheraoxidizing medium. Also, 7 during use the catalyst gradually undergoes a permanent deactivation .I-which' acannot be counteractedby any known regeneration treatment. When the catalyst .decli-nes toa given level, it is necessary to discard it and substitute In the {catalystsof the typewin. question .-:the activity is more i or less proportional to the.:concentration-oi 'themolybdenum oxide on t'o a certain point. "Thus,'for example; ini hydrofi -forming the activity -of :theca'talyst "increases with increase=-in -molybdenulmcontent uD,-.f;t0 about a point where the concentration -of -molybdenum oxide corresponds-to about. 4x10? grams per square meter of surface of the alumina. Inthe preferred alumina of -:the type: described above-where the available surface usually ein (as --measL u'ed--bynitrogen adsorption), I this corresponds --to about 6 by=-wei ghtof --molybdenum. While lower concentrations one lower activities, higher concentrations giveabout- -the same activity. Consequently,- -n hydroforming practice the catalysts-ue adjusted 4:0- contain l about 6% oi molyb'denum. 5K Inthe above--the best-.---rnelybdena-a;lmnina catalysts of the art-have been described-in detail and the reasons a); the various steps 5 and choices have been pointed---out. -We :have new made the unexpectedfinding-that certain -of the steps novwemployed--are=-'detrimental rather than advantageous and; that these --catalysts be ystill further greatly improved by'certain changes -in-the-cataly st preparation. by certain changes in the rnthodsof preparation and by certain combinationsof-stepshit is -possibleto produce catalysts; of the described ;type which are not only more aotiveg-bue are-inorestable against loss of;activitywith heat and use, and 'are-=f -urthermore more stable against -loss- 'of mechanical I strength; with heatan use; -These advantages are of'the; utmost importance, particularly' in-hydroforming. V

The improved catalystspf -the-present-inyentionevolved zfrom ce'rtain combinations oi-;find- -ings--which--willbeexplained. ous-moms :eub

:stantiate our previous findings, and also those of the art, that the preferred alumina is the above-described massive adsorptive alumina, preferably in gamma form, prepared by the dehydration of alumina crystallized from alkaline aluminate solutions. Our findings are also in complete agreement with the following facts, explained above:

(1) That adsorptive alumin'as upon being subjected to the elevated temperatures encountered in various vapor phase processes, particularly during the periodic regeneration treatments are slowly converted into the inactive alpha modifications.

(2) That in the presence of molybdenum oxide this transformation (1) takes place at temperatures encountered in use. resulting in deactivation of the catalysts.

(3) That the transformation of alumina into the inactive alpha alumina in the presence of molybdenum oxide takes place in two steps, to wit: the formation of a compound of the molybdena and alumina, and the resolution of this compound into molybdena and alpha alumina.

(4) That adsorptive aluminas of the preferred type which are prepared from aluminas precipitated from alkaline aluminate solutions and thus contain appreciable quantities (0.5% to 1.25%) of alkali metal (sodium) salts intimately associated with the alumina are per so more difficult to;

convert to the alpha modification by heating.

We have found, however, (1) that in the presence oi molybdena the conversion of the alumina to alpha alumina is catalyzed by traces of alkali metal salts, and (2) that if the content of alkali metal salts invariably present in the preferred alumnas is reduced to a certain critical maximum this undesirable deactivation mechanism is substantially prevented. "Thus, contrary to expectation, by employing aluminas of the preferred type, from which the alkali metal salts have been removed down to below a certain criticalmaximum, catalysts may be prepared which maintain their activity in use for much longer periods of time. We have, furthermore, found that cataiii lysts prepared with aluminas from which the alkali metal salts, which are invariably present, have been removed down to this certain critical maximum are also much superior to the hithertoemployed catalysts in that they afford much I greater production capacities per volume of catalyst. The critical maximum amount of alkali metal mentioned above is about 1.11 10"' grams per square meter of surface of the alumina as measured by nitrogen. Thus, in the preferred-,

aluminas of the type now used in which the area is approximately 150 m. /g., the critical maximum content of sodium is about 0.17%. As explained above, the sodium of other alkali metal in the alumina is intimately bound due to the crystal! lization of the base alumina from alkali alumi-" nate solutions. While we do not intend to be bound by the correctness of the statement, all available evidence indicates that the alkali metal presentafter the alkali metal content has been;

. preferred type of alumina, from which the con- .8 tent of alkali metal (sodium) invariably present has been removed down to below the given critical maximum, is illustrated in the following examples.

EXAMPLE I A molybdena-alumina catalyst was prepared starting with a 2-4 mesh massive adsorptive alumina obtained from an alumina trlhydrate which was crystallized from a sodium aluminate solution. This alumina was partially dehydrated to about 6% H2O, contained about 0.33% Na, and had an active surface of approximately 180 mi /g. The alumina in this condition was washed with a 0.1 molar solution of aluminum nitrate at room temperature until the concentration of sodium was reduced to 0.07%. It was then washed with water and dried, and finally heated at 700 C. for 6 hours to further dehydrate it largely into the gamma form. It was then soaked in an excess of a solution of ammonium molybdate (12.9% molybdenum) at room temperature for 5 hours. The excess solution was drained and the impregnated alumina dried at C. and heated at 500 C. for 2 hours to convert the ammonium molybclate to molybdenum oxide. The catalyst contained 6.09% molybdenum. This catalyst was tested for the hydroforming of a commercial straight run petroleum fraction containing a considerable concentration of methyl cyclohexane under the following practical hydroforming conditions:

Temperature 490 C. Pressure 20 atmospheres Liquid hourly space velocity 0.65, 1.5 and 2.5 Mols diluent gas/moi of hydrocarbon feed 5:1 (50% H2) standard hydroforming catalyst prepared with the same type of, base alumina are given.

' Table I Per cent of arcmatic hydrocarbans in the liquid product by volume Liquid hourly space velocity 0.65 1.5 2.6

Standard catalyst 55.4 43.9 35. Improved catalyst 69.3 64.7 Table II Yield of aromatic hydrocarbons, per cent by volume of the (eed Liquid hourly space velocity 0.65 1.5 2.5

Standard catalyst 46.4 39.6 32. Improved catalyst 50.5 46.6 38.?

It will be observed that the activity and efficiency of the improved catalyst of the invention is considerably above that of the standard catalyst which is representative of the best catalyst of the type hitherto known in the art. This improvement is furthermore considerably greater than it'miht-"appar from consideration "of the increased weave s-ioris obtairied since the improved eatalyst lie "ernpltiye'd at a space "velocity of about '6 to give sub'stantially equivalent GO'IIV''i'S'iOri f at the coi-n'mercial 's'p' eldeit'y f 0.65. Thus, it is' seen that lo y -the a'ppl ation-of the i-rnproved catalyst oftheinvention theiproductive' capacity -per catalytic converter may 1 be increased i about "During use molybdena aluniina catalystsg'ra'dua lly lindergo a certain deactivation and usually a loss in 'iiiechanicafstre'rith. Thisfit has been "round, 'is due primarily to 'the relatively -hig h temperatures 't'o whichthe catalyst is suhjcted, pa'rti'cularlyin the riensratibn treatment. I The ability of the 'catalyststvmamtain their 'aetil'lity and strength'is therefore determined by their meat "stability, A heat tr'eatiii'ent "at 'a temperature'of 8005C. rem-permeat- 6 hours corresponds approximatelytoaperioti of about 3 4 months of use under average normal conditions in the plant. The above-described standard catalyst and the improvedcatalyst-describedin Example I were subjected to this heat treatment and then tested. with respect to hydroforming activity under the eonditiohs described in EXample I.

The activities, expressed as yields of aromatics in per cent by volume of the the following Table III.

time if! feed, are given -in Yield Liquid hourly space velocity" s tfie standar'd catalyst Comparing Table with 'Table II it is seen that whereas the standard -"c atalyst lost sub'stantial-lyallof its activity *(the'iriitiahfeed contained about by volume-of aromatics) ,the improved catalyst lost comparatively little activity. Thus, the improved catalyst after this heat treatment, which, as explained, is equivalent to 8-4 months of use, was still more active than the fresh standard catalyst. y H I 'Ihe removal of the sodium and/or other alkali metal salts invariably .present in the alumina's aeriveurrom alkaline aluminate solutions is di'ificult, 'es'peciallyin the case "of the massive haustive washing, trreratiy with an acid such, for instance, a sja dilute STJIlItfOh 'of hydrochloric acid, nitric acid, acetic "acid, er the like, having a pH preferably of 4 or below. Sulfuric acid "less suitable since sulfates left in the alumina are harmful. fiyarafiuc "0 acre and similarly acting nudnaes are also iess suitable since ameafa ers ticularly suitable"polyvalentintal salts are, for

example, aluminum nitrate "and aluminum chloride; other suitable fsalts 6r 'pglyval'ent metals Which dofnot mutate; "undesired cations or anions into the 'at alystlmay' also be employed.

Thus, for example,"thealumina'rnay be treated with a dilute solution of aluminum 'nit'r'ate or aluminum chloride, Ihis treatment generally requires several hoursitdremove'the alkali metal to the desired'lowmaximum concentration but be 'hast mes' somewnat heat and agitation. 'After tlh'e "treatmenttb remove the alkali metal salts, eith'enwithacidsolutions or by'salt solutions, it is desirable, but not essential, to give thealuinina afinal'washinlg treatment with Wa r. r

In order to bring the concentration of the alkalrrne'tal down "to the" critical 'm'aximum it is advantageous. that the above-described treatments be effected while the aluminais in 'an active state, llvhen th'e caitalystfistobe prepared "with "the alumina in a stateof hydration corresponding approximately fto the alpha monohythe alkali metal salts "f antageously first deand then subjected merits to remove rom he arge accessible e alkali metalcont'ent is inner surface uritil 'j't .d'o iajan efa il 'f y i v njc' limit. When theca'talystistojbe prepared with advantageous when the alumina largely in gamma form (having less than about" 5% H2O as determined by loss on ignition) the'aliirnina may "also be dehydrated to theds ired e'gteritfahd then subjected to one or more suitable treatments to remove the alkali metal to the indicated extent. It is, however, v A p ploy in'ggamrna alumina to 'first partially 'dehjydrate the ialumina, for instance, down'to a-wate -tqntjent'orabout 5%-14%.

treat it :to remgvefalltali metal salts, and then further ehydra' e it 'to'the desired finals'tate of dehydration. The treasonforj thls is that the partially dehydratedfaluiiiina has a larger ac- 'ciessible inner surface (usually the order of 150 200 square meters per Efrain) and consequently the content ofthe alkali metalsalts may be more easily and fefie'ctively reduced. If the removal *of the alkali metal salts in such treatmam is sufficiently complete,it is not neces'sary t'ojtre'a't the ammma agam after "completing the dehydration. A treatmeritof the alumina after completing the dehydration is, however, advantageous since it appens. that traces of the inaccessible alkali metal "salts remainingafter the fi'rst treatment are 'rehdered accessible in the final dehydration step,

As indicated above, very important properties of molybdena alumina catalysts which are gen erany given insufficient con'si'de'ration are the 'inechanic'al strength 'and'the ability to retain the mechanical strength upon use. The preferred catalysts of the-prior art described in detail above have excellent and suificient initial mechanical strength. During use, however, they lose their mechanical strength and tend to become friable. This leads to crumblingplugging and channeling. It is not-intended to conyey the impression that the better prior art catalysts prepared with the above-described preferred type of alumina are ififsu e uv ta9l ,..mq han l y t :be pr fabl. Their lack of really good stability with regard to mechanical strength may be, however, a controlling factor, particularly with regard to the size and shape of the catalyst beds in which they may be practically applied. We have found that the stability of molybdena-alumina catalysts to retain their mechanical stability even after being heated at temperatures higher than usually encountered for any extensive periods in use may be greatly improved by varying the methods of preparation. As explained above, the accepted method of impregnating the alumina with the molybdenum oxide is to impregnate it with such an amount of a solution of a suitable molybdenum compound in such concentration that the entire amount of solution is taken up (absorbed) by the alumina and supplies the exact total amount of the molybdenum salt applied. The reasons for the use of this method have been pointed out. It is now quite unexpectedly found that catalysts having materially greater stability with respect to mechanical strength (hereinafter referred to as mechanical stability as distinguished from catalytic stability) result if the impregnation is effected by soaking the alumina in an excess of a solution of the molybdenum salt of such a concentration that the desired amount of molybdenum is impregated.

The alumina is impregnated with a solution of a suitable molybdenum. compound convertible to the oxide by heating. A particularly suitable compound is, for example, ammonium molybdate. The solution of the molybdenum compound is employed in a quantity suflicient to completely cover the alumina when the latter is saturated and the amount of molybdenum adsorbed is controlled by adjusting the concentration of molybdenum in the solution. This may require carefully controlling the adsorptive capacity of the alumina and/or individual tests for each batch of alumina. As will be seen, however, the advantage gained far outweighs this inconvenience, The excess solution of the molybdenum compound is then drained and the alumina dried and calcined in the usual manner to convert the molybdenum compound to molybdenum oxide. The excess solution of the molybdenum compound may be reused after adding a further amount of water and a sufiicient amount of the molybdenum compound to bring the molybdenum concentration to the desired level. Due to traces of impurities, it may be necessary to discard the drained excess solution of the molybdenum compound after the preparation of a number of batches of catalyst. It will be seen, however, that this disadvantage is far outweighed by the superiority of the product obtained. It is not known why this method of impregnation gives such an unexpected difference but it is believed that it may be due to the fact that in this method of impregnatiOn the molybdenum is much more evenly distributed in the alumina particles. The catalysts prepared from aluminas of the alkalicontaining type from which the alkali metal has been removed down to the given critical limits, even when impregnated by the conventional method, have mechanical stabilities as good as those now commercially. used. Their mechanical stability is, however, improved by the described method of impregnation.

EXAMPLE III A series of catalysts was prepared starting with granules of massive adsorptive alumina obtained by the partial dehydration of an alumina trihydrate which was crystallized from a sodium aluminate solution. The alumina inthe active, partially dehydrated state was treated as described to reduce the concentration of sodium to about 0.07% by weight. The substantially sodium-free alumina was then further dehydrated to convert it largely into the gamma form and impregnated in the described preferred manner with excess solutions of ammonium molybdate to produce a series of similar catalysts having difierent concentrations of molybdenum. These catalysts were then applied in a hydroforming treatment under the same conditions (LI-ISV=0.65) and with the same hydrocarbon ieed as shown in Example I. Portions of the catalysts were also heated at 800 C. for six hours as described above to rapidly bring them to a state of decline comparable with 3-4 months of continuous use under these conditions, and these portions were then also applied in the hydroforming treatment. The activities found, expressed in terms of the aromatic yield based on the feed, are given in the following table:

Table IV Yield of Aromatics Per Cent Based on the Feed olyb- Catalyst denum Fresh Catalyst Catalyst In the above we have described in detail how molybdena-alumina catalysts, prepared with various alkali-containing aluminas, may be increased in activity and greatly increased in catalytic stablity by suitably removing the alkali metal salts to a certain critical maximum concentration, may be increased in mechanical stability by changing the method of impregnation, and how molybden'a-alumina catalystsprepared with var- =ious alkali-containing aluminas from which a1- kali metals have been removed to certain limits, may be greatly increased in mechanical stability by adjusting the concentration of molybdena. The first improvement may be applied independently. The second improvement may be applied independently, or in conjunction with the ifirst improvement, in which case the concentration of molybdenum may vary over a considerable range and/or in conjunction with the first and third improvement to aflford accumulated benefits.

Having now particularly described the nature of the said invention and in what manner the ing particles with a liquid capable of removing sodium values therefrom.

2. The process of producing alumina of low soda content from particles of alumina hydrate obtained from a sodium aluminate solution comprising the steps of calcining the particles of aluminum hydrate sufficiently to remove only a part of the chemically combined water therefrom, subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom, thereafter calcining said particles sufficiently that the total water content thereof is lower than the water content of the particles at the end of said first-mentioned cal cination, and subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom.

3. The process of producing alumina of low soda content from particles of aluminum hydrate containing soda comprising the steps of calcining the particles of aluminum hydrate to reduce the water content to between about 6% and about 14%, subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom, thereafter calcining said particles suiiiciently that the total water content thereof is lower than the water content of the particles at the end of said first-mentioned calcination, and subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom.

4. The process of producing alumina of low soda content from particles of aluminum hydrate containing soda comprising the steps of calcining the particles of aluminum hydrate sufficiently to remove only a part of the chemically combined Water therefrom, subsequently leaching the resulting particles with a liquid. capable of removing sodium values therefrom until the content of soda is below 1.1l lgrams per square meter of surface of the alumina, thereafter calcining said particles sufficiently that the total water content thereof is lower than the water content of the particles at the end of said firstmentioned calcination, and subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom.

5. The process of producing alumina of low soda content from particles of aluminum hydrate containing soda comprising the steps of calcining the particles of aluminum hydrate sufficiently to remove only a part of the chemically combined water therefrom, subsequently leaching the resulting particles with an aqueous solution of an aluminum salt to remove sodium values therefrom, thereafter calcining said particles sufiicient- 1y that the total water content thereof is lower than the water content of the paricles at the end of said first mentioned calcination, and subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom.

6. The process of producing alumina of low soda content from particles of aluminum hydrate containing soda comprising the steps of calcining the particles of aluminum hydrate sufficiently to remove only a part of the chemically combined water therefrom subsequently leaching the resulting particles with a liquid capable of removing sodium values therefrom, thereafter calcining said particles sufiiciently that the alumina is largely dehydrated to gamma alumina, and sub= sequently leaching the resulting particles with a liquid capable of removing sodium values therefrom.

MIROSLAV W. TAM'ELE. VANAN C. IRVINE. JAMES F. MAHAR.

No references cited. 

